Dengjun Wang

Transport of Biochar Particles in Saturated Granular Media: Effects of Pyrolysis Temperature and Particle Size

Land application of biochar is increasingly being considered for potential agronomic and environmental benefits, e.g., enhancing carbon sequestration, nutrient retention, water holding capacity, and crop productivity; and reducing greenhouse gas emissions and bioavailability of environmental contaminants. However, little is known about the transport of biochar particles in the aqueous environment, which represents a critical knowledge gap because biochar particles can facilitate the transport of adsorbed contaminants. In this study, column experiments were conducted to investigate biochar particle transport and retention in water-saturated quartz sand. Specific factors considered included biochar feedstocks (wheat straw and pine needle), pyrolysis temperature (350 and 550 °C), and particle size (micrometer-particle (MP) and nanoparticle (NP)). Greater mobility was observed for the biochars of lower pyrolysis temperatures and smaller particle sizes. Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) calculations that considered measured zeta potentials and Lewis acid-base interactions were used to better understand the influence of pyrolysis temperature on biochars particle transport. Most biochars exhibited attractive acid-base interactions that impeded their transport, whereas the biochar with the greatest mobility had repulsive acid-base interaction. Nonetheless, greater retention of the MPs than that of the NPs was in contrast with the XDLVO predictions. Straining and biochar surface charge heterogeneity were found to enhance the retention of biochar MPs, but played an insignificant role in the biochar NP retention. Experimental breakthrough curves and retention profiles were well-described using a two-site kinetic retention model that accounted for depth-dependent retention at one site. Modeled first-order retention coefficients on both sites 1 and 2 increased with increasing pyrolysis temperature and particle size.

Humic Acid Facilitates the Transport of ARS-Labeled Hydroxyapatite Nanoparticles in Iron Oxyhydroxide-Coated Sand

Hydroxyapatite nanoparticles (nHAP) have been widely used to remediate soil and wastewater contaminated with metals and radionuclides. However, our understanding of nHAP transport and fate is limited in natural environments that exhibit significant variability in solid and solution chemistry. The transport and retention kinetics of Alizarin red S (ARS)-labeled nHAP were investigated in water-saturated packed columns that encompassed a range of humic acid concentrations (HA, 0-10 mg L(-1)), fractional surface coverage of iron oxyhydroxide coatings on sand grains (λ, 0-0.75), and pH (6.0-10.5). HA was found to have a marked effect on the electrokinetic properties of ARS-nHAP, and on the transport and retention of ARS-nHAP in granular media. The transport of ARS-nHAP was found to increase with increasing HA concentration because of enhanced colloidal stability and the reduced aggregate size. When HA = 10 mg L(-1), greater ARS-nHAP attachment occurred with increasing λ because of increased electrostatic attraction between negatively charged nanoparticles and positively charged iron oxyhydroxides, although alkaline conditions (pH 8.0 and 10.5) reversed the surface charge of the iron oxyhydroxides and therefore decreased deposition. The retention profiles of ARS-nHAP exhibited a hyperexponential shape for all test conditions, suggesting some unfavorable attachment conditions. Retarded breakthrough curves occurred in sands with iron oxyhydroxide coatings because of time-dependent occupation of favorable deposition sites. Consideration of the above effects is necessary to improve remediation efficiency of nHAP for metals and actinides in soils and subsurface environments.

Facilitated transport of Cu with hydroxyapatite nanoparticles in saturated sand: Effects of solution ionic strength and composition

Column experiments were conducted to investigate the facilitated transport of Cu in association with hydroxyapatite nanoparticles (nHAP) in water-saturated quartz sand at different solution concentrations of NaCl (0-100 mM) or CaCl(2) (0.1-1.0 mM). The experimental breakthrough curves and retention profiles of nHAP were well described using a mathematical model that accounted for two kinetic retention sites. The retention coefficients for both sites increased with the ionic strength (IS) of a particular salt. However, the amount of nHAP retention was more sensitive to increases in the concentration of divalent Ca(2+) than monovalent Na(+). The effluent concentration of Cu that was associated with nHAP decreased significantly from 2.62 to 0.17 mg L(-1) when NaCl increased from 0 to 100 mM, and from 1.58 to 0.16 mg L(-1) when CaCl(2) increased from 0.1 to 1.0 mM. These trends were due to enhanced retention of nHAP with changes in IS and ionic composition (IC) due to compression of the double layer thickness and reduction of the magnitude of the zeta potentials. Results indicate that the IS and IC had a strong influence on the co-transport behavior of contaminants with nHAP nanoparticles.

Antagonistic Effects of Humic Acid and Iron Oxyhydroxide Grain-Coating on Biochar Nanoparticle Transport in Saturated Sand

Biochar land application may result in multiple agronomic and environmental benefits (e.g., carbon sequestration, improving soil quality, and immobilizing environmental contaminants). However, our understanding of biochar particle transport is largely unknown in natural environments with significant heterogeneity in solid (e.g., patches of iron oxyhydroxide coating) and solution chemistry (e.g., the presence of natural organic matter), which represents a critical knowledge gap in assessing the environmental impact of biochar land application. Transport and retention kinetics of nanoparticles (NPs) from wheat straw biochars produced at two pyrolysis temperatures (i.e., 350 and 550 °C) were investigated in water-saturated sand columns at environmentally relevant concentrations of dissolved humic acid (HA, 0, 1, 5, and 10 mg L(-1)) and fractional surface coverage of iron oxyhydroxide coatings on sand grains (ω, 0.16, 0.28, and 0.40). Transport of biochar NPs increased with increasing HA concentration, largely because of enhanced repulsive interaction energy between biochar NPs and sand grains. Conversely, transport of biochar NPs decreased significantly with increasing ω due to enhanced electrostatic attraction between negatively charged biochar NPs and positively charged iron oxyhydroxides. At a given ω of 0.28, biochar NPs were less retained with increasing HA concentration due to increased electrosteric repulsion between biochar NPs and sand grains. Experimental breakthrough curves and retention profiles were well described using a two-site kinetic retention model that accounted for Langmuirian blocking or random sequential adsorption at one site. Consistent with the blocking effect, the often observed flat retention profiles stemmed from decreased retention rate and/or maximum retention capacity at a higher HA concentration or smaller ω. The antagonistic effects of HA and iron oxyhydroxide grain-coating imparted on the mobility of biochar NPs suggest that biochar colloid transport potential will be dependent on competitive influences exerted by a number of environmental factors (e.g., natural organic matter and metal oxides).

Modeling the transport of TiO2 nanoparticle aggregates in saturated and unsaturated granular media: Effects of ionic strength and pH

This study aims to explore the mechanisms governing the transport and retention kinetics of TiO(2) nanoparticle aggregates (NPAs) in flow-through columns of packed sand, particularly under unsaturated conditions. The study was carried out at different pHs (2.6, 7.1, and 9.6) and ionic strengths (ISs) (1.0, 10, and 50 mM). A two-site kinetic attachment model was used to describe transport behaviors of TiO(2) NPAs. At low ISs (i.e., 1.0 and 10 mM) and in neutral/alkaline conditions, high mobility of TiO(2) NPAs was observed in both saturated and unsaturated conditions. However, the retention of TiO(2) NPAs was substantially enhanced at the high IS (50 mM) and in extremely acidity condition (pH = 2.6), because of increased aggregation and straining of TiO(2) NPAs during their transport course. The breakthrough curves (BTCs) of TiO(2) NPAs under unsaturated and saturated conditions almost overlapped, suggesting that decreasing the water saturation did not enhance the retention of TiO(2) NPAs in sand columns. This was probably due to the repulsive interactions existed between negatively charged air-water and TiO(2) NPAs systems that resulted in unfavorable attachment conditions. The two-site kinetic attachment model provided a good description for the BTCs of TiO(2) NPAs both in saturated and unsaturated conditions. The fitted parameters could successfully explain the transport behaviors of TiO(2) NPAs under various solution chemistries.

Hyperexponential and nonmonotonic retention of polyvinylpyrrolidone-coated silver nanoparticles in an Ultisol.

The increasing application of engineered nanoparticles (ENPs) has heightened the concern that these ENPs would eventually be released to the environment and may enter into life cycle of living beings. In this regard, it is essential to understand how these ENPs transport and retain in natural soils because they are considered to be a major repository for ENPs. Herein, transport and retention of polyvinylpyrrolidone (PVP)-coated silver nanoparticles (PVP-AgNPs) were investigated over a wide range of physicochemical factors in water-saturated columns packed with an Ultisol rich in clay-size particles. Higher mobility of PVP-AgNPs occurred at larger soil grain size, lower solution ionic strength and divalent cation concentration, higher flow rate, and greater PVP concentrations. Most breakthrough curves (BTCs) for PVP-AgNPs exhibited significant amounts of retardation in the soil due to its large surface area and quantity of retention sites. In contrast to colloid filtration theory, the shapes of retention profiles (RPs) for PVP-AgNPs were either hyperexponential or nonmonotonic (a peak in particle retention down-gradient from the column inlet). The BTCs and hyperexponential RPs were successfully described using a 1-species model that considered time- and depth-dependent retention. Conversely, a 2-species model that included reversibility of retained PVP-AgNPs had to be employed to better simulate the BTCs and nonmonotonic RPs. As the retained concentration of species 1 approached the maximum solid-phase concentration, a second mobile species (species 2, i.e., the same PVP-AgNPs that are reversibly retained) was released that could be retained at a different rate than species 1 and thus yielded the nonmonotonic RPs. Some retained PVP-AgNPs were likely to irreversibly deposit in the primary minimum associated with microscopic chemical heterogeneity (favorable sites). Transmission electron microscopy and energy-dispersive X-ray spectroscopy analysis suggested that these favorable sites were positively charged sites on montmorillonite edges and goethite surfaces in the soil. Overall, our study highlights that the transport and especially retention of PVP-AgNPs are highly sensitive to the physicochemical factors, but mathematical modeling can accurately predict the fate of these ENPs in porous media which is important for better understanding the fate of these ENPs in point of exit and in the environment.

Transport behavior of humic acid-modified nano-hydroxyapatite in saturated packed column: effects of Cu, ionic strength, and ionic composition.

The surfaces of nano-hydroxyapatite (nHAP) used for contaminated soil and groundwater remediation may be modified to render nHAP highly mobile in the subsurface. Humic acid (HA) is widely used to modify and stabilize colloid suspensions. In this work, column experiments were conducted to determine the effects of contaminant (e.g., Cu) concentration, ionic strength (IS), and ion composition (IC) on the transport behavior of HA-modified nHAP in saturated packed columns. IS and nature of the cation had strong effects on the deposition of nHAP, and the effect was greater for divalent than for monovalent cations. Divalent cations have a greater capacity to screen the surface charge of nHAP, and Ca(2+) bridges the HA-modified nHAP colloidal particles, which causes greater deposition. Moreover, Cu(2+) had a greater effect on the transport behavior than Ca(2+) due to their strong exchange with Ca(2+) of nHAP and its surface complexation with nHAP. The relative travel distance L(T), of the injected HA-modified nHAP colloids, ranges from less than one to several meters at varying Cu concentrations, ISs, and ICs in saturated packed columns. The results are crucial to evaluate the efficacy of nHAP on the remediation of contaminated soil and groundwater environments.

Facilitated Transport of Copper with Hydroxyapatite Nanoparticles in Saturated Sand

375 Soil Sci. Soc. Am. J. 76:375–388 Posted online 20 Dec. 2011 doi:10.2136/sssaj 2011.0203 Received 3 June 2011 *Corresponding author (dmzhou@issas.ac.cn)

Transport of ARS-labeled hydroxyapatite nanoparticles in saturated granular media is influenced by surface charge variability even in the presence of humic acid

Hydroxyapatite nanoparticle (nHAP) is increasingly being used to remediate soils and water polluted by metals and radionuclides. The transport and retention of Alizarin red S (ARS)-labeled nHAP were investigated in water-saturated granular media. Experiments were carried out over a range of ionic strength (I(c), 0-50mM NaCl) conditions in the presence of 10 mg L(-1) humic acid. The transport of ARS-nHAP was found to decrease with increasing suspension I(c) in part, because of enhanced aggregation and chemical heterogeneity. The retention profiles (RPs) of ARS-nHAP exhibited hyperexponential shapes (a decreasing rate of retention with increasing transport distance) for all test conditions, suggesting that some of the attachment was occurring under unfavorable conditions. Surface charge heterogeneities on the collector surfaces and especially within the ARS-nHAP population were contributing causes for the hyperexponential RPs. Consideration of the effect(s) of I(c) in the presence of HA is needed to improve the efficacy of nHAP for scavenging metals and actinides in real soils and groundwater environments.

Composite Inorganic Polymer Flocculants

The main components of composite inorganic polymer flocculants are the Al, Fe and Si compounds. They can be hydroxylized individually before combination or afterwards when they are mixed together.